Formable Sheets for Medical Applications and Methods of Manufacture Thereof

ABSTRACT

Disclosed herein is an appliance for use in an oral cavity, wherein the appliance comprises a polymeric shell that comprises a polymeric mixture, and further wherein the polymeric shell has cavities designed to receive teeth. Disclosed herein too is a method for maintaining or repositioning teeth in the oral cavity comprising placing an appliance in a patient&#39;s mouth, wherein the appliance comprises a polymeric shell that comprises a polymeric mixture, and further wherein the polymeric shell has cavities designed to receive teeth.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a division of U.S. application Ser. No. 10/705,590filed Nov. 10, 2003, the entire contents of which are incorporatedherein by reference.

BACKGROUND

This disclosure relates to formable sheets for medical applications andmethods of manufacture thereof.

Repositioning teeth for aesthetic or other reasons is generallyaccomplished by wearing devices called “braces”. Braces comprise avariety of components such as brackets, archwires, ligatures, andO-rings. Attaching these components to a patient's teeth is a tediousand time-consuming procedure requiring many meetings with the treatingorthodontist. This reduces the orthodontist's patient capacity and thusmakes orthodontic treatment quite expensive.

The primary force-inducing component in a set of braces is the archwire.The archwire is resilient and is attached to the brackets by way ofslots in the brackets. The archwire links the brackets together andexerts forces on them to move the teeth over time. Twisted wires orelastomeric O-rings are generally used to reinforce attachment of thearchwire to the brackets. Attachment of the archwire to the brackets iscalled “ligation” and wires used in this procedure are called“ligatures.” The elastomeric O-rings are called “plastics.”

After the archwire is in place, periodic meetings with the orthodontistare required, during which the patient's braces will be adjusted byinstalling a different archwire having different force-inducingproperties or by replacing or tightening existing ligatures. Thesemeetings are generally scheduled every three to six weeks.

As detailed above, the application of braces to patient's teeth is atedious and time consuming process and requires many visits to theorthodontist's office. Further, the use of braces is unsightly,aesthetically unpleasing, uncomfortable, presents a risk of infection,and makes brushing, flossing, and other dental hygiene proceduresdifficult. For these reasons, it is desirable to provide alternativemethods and systems for repositioning the teeth.

SUMMARY

Disclosed herein is an appliance for use in an oral cavity, wherein theappliance comprises a polymeric shell that comprises a polymericmixture, and further wherein the polymeric shell has cavities designedto receive teeth.

Disclosed herein too is a method for maintaining or repositioning teethin the oral cavity comprising placing an appliance in a patient's mouth,wherein the appliance comprises a polymeric shell that comprises apolymeric mixture, and further wherein the polymeric shell has cavitiesdesigned to receive teeth.

Disclosed herein too is a method for maintaining or repositioning teethin the oral cavity comprising placing an appliance in a patient's mouth,wherein the appliance comprises a polymeric shell that comprises apolymeric mixture, and further wherein the polymeric shell has cavitiesdesigned to receive teeth.

The above-described and other features will be appreciated andunderstood by those skilled in the art from the following detaileddescription, drawings, and appended claims.

DESCRIPTION OF FIGURES

FIG. 1 illustrates a patient's jaw and provides a general indication ofhow teeth may be moved by the appliance;

FIG. 2 illustrates a single tooth from FIG. 1 and defines how toothmovement distances are engineered;

FIG. 3 illustrates the jaw of FIG. 1 together with an incrementalposition adjustment appliance;

FIG. 4 is a block diagram illustrating the steps for producing a systemof incremental position adjustment appliances; and

FIG. 5 illustrates alternative processes for producing a plurality ofappliances utilizing digital data sets representing the intermediate andfinal appliance designs.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

Disclosed herein is an appliance made from a sheet comprising apolymeric mixture that may be advantageously used for repositioningteeth from an initial tooth arrangement to a final tooth arrangement. Inone embodiment, the appliance displays properties of optical clarity,stain resistance, and transparency, which makes the appliance invisiblewhen used in the oral cavity. The appliance is also easy to install andis more comfortable to wear than braces. The polymeric mixture used inthe appliance displays properties of toughness and creep resistance,which facilitates the incremental repositioning of individual teeth in aseries of less than or equal to about 40 steps, preferably less than orequal to about 25 steps, more preferably less than or equal to about 10steps, and even more preferably less than or equal to about 5 steps.

The polymeric mixtures may also be advantageously used in other medicaldevices as well as in other dental applications such as dental retainerappliances that may be used for retaining teeth in a desired positionand other devices that can be used to prevent patients from grindingtheir teeth during their sleep. In one embodiment, the polymer mixturemay be used to manufacture an appliance for use in an oral cavity,wherein the appliance comprises a polymeric shell that has cavitiesdesigned to receive teeth. In another embodiment, the appliance is partof a system of appliances designed to reposition teeth in a series ofsteps. In yet another embodiment, the polymeric shell comprises two ormore layers, wherein on layer comprises an elastomer.

A “step” refers to one use of the appliance for a prescribed period oftime on either the upper or lower teeth to facilitate either therepositioning of the teeth or the retaining of the teeth in a particularposition. The term “teeth” as defined herein may apply to a single toothor to a plurality of teeth.

The successive use of a number of such appliances permits each applianceto be configured to move individual teeth in small increments. Adesirable increment for movement of the teeth is less than or equal toabout 2 mm, preferably less than or equal to about 1 mm, and morepreferably less than or equal to about 0.5 mm. These increments refer tothe maximum linear translation of any point on a tooth as a result ofusing a single appliance. The movements provided by successiveappliances, may not be the same for any particular tooth. Thus, onepoint on a tooth may be moved by a particular distance as a result ofthe use of one appliance and thereafter moved by a different distanceand/or in a different direction by the use of a later appliance.

Referring now to FIG. 1, a representative jaw 100 generally contains upto sixteen teeth 102. The appliance may be used to move at least some ofthese teeth from an initial tooth arrangement to a final tootharrangement. To understand how the teeth may be moved, an arbitrarycenterline (CL) is drawn through one of the teeth 102. With reference tothis centerline (CL), the teeth may be moved in the orthogonaldirections represented by axes 104, 106, and 108 (where 104 is thecenterline). The centerline may be rotated about the axis 108 (rootangulation) and 104 (torque) as indicated by arrows 110 and 112,respectively. Additionally, the tooth may be rotated about thecenterline, as represented by arrow 114. Thus, all possible free-formmotions of the tooth can be performed.

Referring now to FIG. 2, the magnitude of any tooth movement achieved bythe methods and systems will be defined in terms of the maximum lineartranslation of any point P on a tooth 102. Each point P_(i) will undergoa cumulative translation as that tooth is moved in any of the orthogonalor rotational directions defined in FIG. 1. Thus, an arbitrary point P₁may in fact undergo a true side-to-side translation as indicated byarrow d₁, while a second arbitrary point P₂ may travel along an arcuatepath, resulting in a final translation d₂.

Referring now to FIG. 3, a system for effecting incrementalrepositioning of individual teeth comprises a plurality of incrementalposition adjustment appliances. The appliances are intended to effectincremental repositioning of individual teeth in the jaw and areintended to be worn by a patient successively in order to achieve thegradual tooth repositioning as described herein. A preferred appliance100 will comprise a polymeric shell having a cavity shaped to receiveand resiliently reposition teeth from one tooth arrangement to asuccessive tooth arrangement. The polymeric shell will preferably fitover all teeth present in the upper or lower jaw. Often, only a certaintooth or teeth will be repositioned while other teeth will provide abase or anchor region for holding the repositioning appliance in placeas it applies the resilient repositioning force against the tooth orteeth to be repositioned. In complex cases, however, many or most of theteeth will be repositioned at some point during the treatment. In suchcases, the teeth that are moved can also serve as a base or anchorregion for holding the repositioning appliance. Additionally, the gumsand/or the palette can serve as an anchor region, thus allowing all ornearly all of the teeth to be repositioned simultaneously.

The appliance 100 of FIG. 3 preferably contains at least one layermanufactured from a sheet of a polymeric mixture. Polymeric mixturesused for such appliances, are generally physical mixtures of two or morethermoplastic polymers. Thermoplastic polymers that may be used in thepolymeric mixture may be oligomers, polymers, ionomers, dendrimers,copolymers such as block copolymers, graft copolymers, star blockcopolymers, random copolymers, and the like, as well as combinationscomprising at least one of the foregoing polymers. Suitable examples ofthermoplastic polymers are polyolefins such as polyethylene,polypropylene; polyamides such as Nylon 4,6, Nylon 6, Nylon 6,6, Nylon6, 10, Nylon 6, 12; polyesters such as polyethelene terephthalate (PET),polybutylene terephthalate (PBT),poly(1,4-cyclohexane-dimethanol-1,4-cyclohexanedicarboxylate) (PCCD),poly(trimethylene terephthalate) (PTT),poly(cyclohexanedimethanol-co-ethylene terephthalate) (PETG),poly(ethylene naphthalate) (PEN), poly(butylene naphthalate) (PBN);polyarylates, polyimides, polyacetals, polyacrylics, polycarbonates(PC), polystyrenes, polyamideimides, polyacrylates, polymethacrylatessuch as polymethylacrylate, or polymethylmethacrylate (PMMA);polyurethanes, polyarylsulfones, polyethersulfones, polyarylenesulfides, polyvinyl chlorides, polysulfones, polyetherimides,polytetrafluoroethylenes, polyetherketones, polyether etherketones,polyarylene ethers, polydimethylsiloxane, liquid crystalline polymers,polybenzoxazoles, polyoxadiazoles, polybenzothiazinophenothiazines,polybenzothiazoles, polypyrazinoquinoxalines, polypyromellitimides,polyquinoxalines, polybenzimidazoles, polyoxindoles,polyoxoisoindolines, polydioxoisoindolines, polytriazines,polypyridazines, polypiperazines, polypyridines, polypiperidines,polytriazoles, polypyrazoles, polypyrrolidines, polycarboranes,polyoxabicyclononanes, polydibenzofurans, polyphthalides, polyacetals,polyanhydrides, polyvinyl ethers, polyvinyl thioethers, polyvinylalcohols, polyvinyl ketones, polyvinyl halides, polyvinyl nitriles,polyvinyl esters, polysulfonates, polythioesters, polysulfonamides,polyureas, polyphosphazenes, polysilazanes, and the like, as well ascombinations comprising at least one of the foregoing polymers.Preferred polymeric mixtures are those derived from a polycarbonate,polyesters such as cycloaliphatic polyesters and polyarylates, andpolycarbonate-polydimethylsiloxane copolymers.

Preferred polymeric mixtures derived from mixing polycarbonate andpolyesters are PC-PCCD, PC-PETG, PC-PET, PC-PBT, PC-PCT, PC-PCTG,PC-PPC, PC-PCCD-PETG, PC-PCCD-PCT, PC-PPC-PCTG, PC-PCTG-PETG,PC-polyarylates, and the like, as well as combinations comprising atleast one of the foregoing polymeric mixtures.

As stated above, a preferred polymeric mixture is apolycarbonate-cycloaliphatic polyester mixture. As used herein, theterms “polycarbonate”, “polycarbonate composition”, and “compositioncomprising aromatic carbonate chain units” includes compositions havingstructural units of the formula (I):

in which greater than or equal to about 60 percent of the total numberof R¹ groups are aromatic organic radicals and the balance thereof arealiphatic, alicyclic, or aromatic radicals. Preferably, R¹ is anaromatic organic radical and, more preferably, a radical of the formula(II):-A¹-Y¹-A²-  (II)wherein each of A¹ and A² is a monocyclic divalent aryl radical and Y¹is a bridging radical having zero, one, or two atoms which separate A¹from A². In an exemplary embodiment, one atom separates A¹ from A².Illustrative, examples of radicals of this type are —O—, —S—, —S(O)—,—S(O₂)—, —C(O)—, methylene, cyclohexyl-methylene,2-[2,2,1]-bicycloheptylidene, ethylidene, isopropylidene,neopentylidene, cyclohexylidene, cyclopentadecylidene,cyclododecylidene, adamantylidene, and the like. In another embodiment,zero atoms separate A¹ from A², with an illustrative example beingbisphenol (OH-benzene-benzene-OH). The bridging radical Y¹ can be ahydrocarbon group or a saturated hydrocarbon group such as methylene,cyclohexylidene or isopropylidene.

Polycarbonates may be produced by the Schotten-Bauman interfacialreaction of the carbonate precursor with dihydroxy compounds. Generally,an aqueous base such as (e.g., sodium hydroxide, potassium hydroxide,calcium hydroxide, and the like) is mixed with an organic, waterimmiscible solvent such as benzene, toluene, carbon disulfide, ordichloromethane, which contains the dihydroxy compound. A phase transferagent is generally used to facilitate the reaction. Molecular weightregulators may be added either singly or in admixture to the reactantmixture. Branching agents, described forthwith may also be added singlyor in admixture.

Polycarbonates can be produced by the interfacial reaction of dihydroxycompounds in which only one atom separates A¹ and A². As used herein,the term “dihydroxy compound” includes, for example, bisphenol compoundshaving general formula (III) as follows:

wherein R^(a) and R^(b) each independently represent hydrogen, a halogenatom, or a monovalent hydrocarbon group; p and q are each independentlyintegers from 0 to 4; and X^(a) represents one of the groups of formula(IV):

wherein R^(c) and R^(d) each independently represent a hydrogen atom ora monovalent linear or cyclic hydrocarbon group, and R^(e) is a divalenthydrocarbon group.

Examples of the types of bisphenol compounds that may be represented byformula (III) includes the bis(hydroxyaryl)alkane series such as,1,1-bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane,2,2-bis(4-hydroxyphenyl)propane (or bisphenol-A),2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane,1,1-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)n-butane,bis(4-hydroxyphenyl)phenylmethane,2,2-bis(4-hydroxy-1-methylphenyl)propane,1,1-bis(4-hydroxy-t-butylphenyl)propane,2,2-bis(4-hydroxy-3-bromophenyl)propane, and the like;bis(hydroxyaryl)cycloalkane series such as,1,1-bis(4-hydroxyphenyl)cyclopentane,1,1-bis(4-hydroxyphenyl)cyclohexane, and the like; and the like, as wellas combinations comprising at least one of the foregoing bisphenolcompounds.

Other bisphenol compounds that may be represented by formula (III)include those where X is —O—, —S—, —SO— or —S(O)₂—. Some examples ofsuch bisphenol compounds are bis(hydroxyaryl)ethers such as4,4′-dihydroxy diphenylether, 4,4′-dihydroxy-3,3′-dimethylphenyl ether,and the like; bis(hydroxy diaryl)sulfides, such as 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxy-3,3′-dimethyl diphenyl sulfide, and thelike; bis(hydroxy diaryl) sulfoxides, such as, 4,4′-dihydroxy diphenylsulfoxides, 4,4′-dihydroxy-3,3′-dimethyl diphenyl sulfoxides, and thelike; bis(hydroxy diaryl)sulfones, such as 4,4′-dihydroxy diphenylsulfone, 4,4′-dihydroxy-3,3′-dimethyl diphenyl sulfone, and the like;and the like, as well as combinations comprising at least one of theforegoing bisphenol compounds.

Other bisphenol compounds that may be utilized in the polycondensationof polycarbonate are represented by the formula (V)

wherein, R^(f), is a halogen atom of a hydrocarbon group having 1 to 10carbon atoms or a halogen substituted hydrocarbon group; n is a valuefrom 0 to 4. When n is at least 2, R^(f) may be the same or different.Examples of bisphenol compounds that may be represented by the formula(V), are resorcinol, substituted resorcinol compounds such as 3-methylresorcin, 3-ethyl resorcin, 3-propyl resorcin, 3-butyl resorcin,3-t-butyl resorcin, 3-phenyl resorcin, 3-cumyl resorcin,2,3,4,6-tetrafluoro resorcin, 2,3,4,6-tetrabromo resorcin, and the like;catechol, hydroquinone, substituted hydroquinones, such as 3-methylhydroquinone, 3-ethyl hydroquinone, 3-propyl hydroquinone, 3-butylhydroquinone, 3-t-butyl hydroquinone, 3-phenyl hydroquinone, 3-cumylhydroquinone, 2,3,5,6-tetramethyl hydroquinone, 2,3,5,6-tetra-t-butylhydroquinone, 2,3,5,6-tetrafluoro hydroquinone, 2,3,5,6-tetrabromohydroquinone, and the like; and the like, as well as combinationscomprising at least one of the foregoing bisphenol compounds.

Bisphenol compounds such as2,2,2′,2′-tetrahydro-3,3,3′,3′-tetramethyl-1,1′-spirobi-[IH-indene]-6,6′-diolrepresented by the following formula (VI) may also be used.

The preferred bisphenol compound is bisphenol A.

Typical carbonate precursors include the carbonyl halides, for example,carbonyl chloride (phosgene), carbonyl bromide, and the like; thebis-haloformates, for example, the bis-haloformates of dihydric phenolssuch as bisphenol A, hydroquinone, and the like; the bis-haloformates ofglycols such as ethylene glycol, neopentyl glycol, and the like; thediaryl carbonates, such as diphenyl carbonate, di(tolyl) carbonate,di(naphthyl) carbonate, and the like; and the like, as well ascombinations comprising at least one of the foregoing carbonateprecursors. The preferred carbonate precursor for the interfacialreaction is carbonyl chloride.

Branched polycarbonates are also useful, as well as mixtures of linearpolycarbonate and a branched polycarbonate. The branched polycarbonatesmay be prepared by adding a branching agent during polymerization. Thesebranching agents may comprise polyfunctional organic compoundscontaining at least three functional groups, which may be hydroxyl,carboxyl, carboxylic anhydride, haloformyl, and combinations comprisingat least one of the foregoing branching agents. Specific examplesinclude trimellitic acid, trimellitic anhydride, trimellitictrichloride, tris-p-hydroxy phenyl ethane, isatin-bis-phenol,tris-phenol TC (1,3,5-tris((p-hydroxyphenyl)isopropyl)benzene),tris-phenol PA (4(4(1,1-bis(p-hydroxyphenyl)-ethyl) α,α-dimethylbenzyl)phenol), 4-chloroformyl phthalic anhydride, trimesic acid,benzophenone tetracarboxylic acid, and the like, as well as combinationscomprising at least one of the foregoing branching agents. The branchingagents may be added, for example, in an amount of about 0.05 to about2.0 wt %, based upon the total weight of the polycarbonate.

In one embodiment, the polycarbonate may be produced by a meltpolycondensation reaction between a dihydroxy compound and a carbonicacid diester. Examples of the carbonic acid diesters that may beutilized to produce the polycarbonates are diphenyl carbonate,bis(2,4-dichlorophenyl)carbonate, bis(2,4,6-trichlorophenyl) carbonate,bis(2-cyanophenyl) carbonate, bis(o-nitrophenyl) carbonate, ditolylcarbonate, m-cresyl carbonate, dinaphthyl carbonate, bis(diphenyl)carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate,dicyclohexyl carbonate, and the like, as well as combinations comprisingat least one of the foregoing carbonic acid diesters. The preferredcarbonic acid diester is diphenyl carbonate.

Preferably, the number average molecular weight (M_(n)) of thepolycarbonate is about 500 to about 1,000,000 grams/mole (g/mole).Within this range, it is desirable to have a number average molecularweight of greater than or equal to about 1,000 g/mole, preferablygreater than or equal to about 5,000 g/mole, and more preferably greaterthan or equal to about 10,000 g/mole. Also desirable is a number averagemolecular weight of less than or equal to about 200,000 g/mole,preferably less than or equal to about 100,000 g/mole, more preferablyless than or equal to about 65,000 g/mole, and most preferably less thanor equal to about 40,000 g/mole. An exemplary number average molecularweight for the polycarbonate is about 9,000 g/mole to about 38,000g/mole.

Cycloaliphatic polyesters suitable for use in the polymeric mixtures arethose that are characterized by optical transparency, improvedweatherability, chemical resistance, and low water absorption. It isalso generally desirable that the cycloaliphatic polyesters have goodmelt compatibility with the polycarbonate polymers. Cycloaliphaticpolyesters are generally prepared by reaction of a diol with a dibasicacid or derivative. The diols useful in the preparation of thecycloaliphatic polyesters may be straight chain, branched, orcycloaliphatic, preferably straight chain or branched alkane diols, andmay contain from 2 to 12 carbon atoms.

Suitable examples of diols include ethylene glycol, propylene glycolsuch as 1,2- and 1,3-propylene glycol, and the like; butane diol such as1,3- and 1,4-butane diol, and the like; diethylene glycol,2,2-dimethyl-1,3-propane diol, 2-ethyl, 2-methyl, 1,3-propane diol, 1,3-and 1,5-pentane diol, dipropylene glycol, 2-methyl-1,5-pentane diol,1,6-hexane diol, 1,4cyclohexane dimethanol and particularly its cis- andtrans-isomers, triethylene glycol, 1,10-decane diol, and combinationscomprising at least one of the foregoing diols. Particularly preferredis dimethanol bicyclo octane, dimethanol decalin, a cycloaliphatic diolor chemical equivalents thereof, and particularly 1,4-cyclohexanedimethanol or its chemical equivalents. If 1,4-cyclohexane dimethanol isto be used as the diol component, it is generally preferred to use amixture of cis- to trans-isomes in ratios of about 1:4 to about 4:1.Within this range, it is generally desired to use a ratio of cis- totrans-isomers of about 1:3.

The diacids useful in the preparation of the cycloaliphatic polyesterpolymers are aliphatic diacids that include carboxylic acids having twocarboxyl groups each of which are attached to a saturated carbon in asaturated ring. Suitable examples of cycloaliphatic acids includedecahydro naphthalene dicarboxylic acid, norbornene dicarboxylic acids,bicyclo octane dicarboxylic acids. Preferred cycloaliphatic diacids are1,4-cyclohexanedicarboxylic acid and trans-1,4-cyclohexanedicarboxylicacids. Linear aliphatic diacids are also useful provided the polyesterhas at least one monomer containing a cycloaliphatic ring. Illustrativeexamples of linear aliphatic diacids are succinic acid, adipic acid,dimethyl succinic acid, azelaic acid, and the like, as well ascombinations comprising at least one of the foregoing. Mixtures ofdiacid and diols may also be used to make the cycloaliphatic polyesters.

Cyclohexanedicarboxylic acids and their chemical equivalents can beprepared, for example, by the hydrogenation of cycloaromatic diacids andcorresponding derivatives such as isophthalic acid, terephthalic acid ornaphthalenic acid, in a suitable solvent (e.g., water or acetic acid) atroom temperature and at atmospheric pressure using catalysts such asrhodium supported on a carrier comprising carbon and alumina. They mayalso be prepared by the use of an inert liquid medium wherein an acid isat least partially soluble under reaction conditions and a catalyst ofpalladium or ruthenium in carbon or silica is used.

Generally, during hydrogenation, two or more isomers are obtained inwhich the carboxylic acid groups are in cis- or trans-positions. Thecis- and trans-isomers can be separated by crystallization with orwithout a solvent, for example, n-heptane, or by distillation. Thecis-isomer tends to be more miscible, however, the trans-isomer hashigher melting and crystallization temperatures and is especiallypreferred. Mixtures of the cis- and trans-isomers may also be used, andpreferably when such a mixture is used, the trans-isomer will preferablycomprise at least about 75 wt % and the cis-isomer will comprise theremainder based on the total weight of cis- and trans-isomers combined.When a mixture of isomers or more than one diacid is used, a copolyesteror a mixture of two polyesters may be used as the cycloaliphaticpolyester resin.

Chemical equivalents of these diacids including esters may also be usedin the preparation of the cycloaliphatic polyesters. Suitable examplesof the chemical equivalents of the diacids are alkyl esters, e.g.,dialkyl esters, diaryl esters, anhydrides, acid chlorides, acidbromides, and the like, as well as combinations comprising at least oneof the foregoing chemical equivalents. The preferred chemicalequivalents comprise the diallyl esters of the cycloaliphatic diacids,and the most preferred chemical equivalent comprises the dimethyl esterof the acid, particularly dimethyl-trans-1,4-cyclohexanedicarboxylate.

Dimethyl-1,4-cyclohexanedicarboxylate can be obtained by ringhydrogenation of dimethylterephthalate, and two isomers having thecarboxylic acid groups in the cis- and trans-positions are obtained. Theisomers can be separated, the trans-isomer being especially preferred.Mixtures of the isomers may also be used as detailed above.

The polyester polymers are generally obtained through the condensationor ester interchange polymerization of the diol or diol chemicalequivalent component with the diacid or diacid chemical equivalentcomponent and having recurring units of the formula (VII):

wherein R³ represents an alkyl or cycloalkyl radical containing 2 to 12carbon atoms and which is the residue of a straight chain, branched, orcycloaliphatic alkane diol having 2 to 12 carbon atoms or chemicalequivalents thereof; and R⁴ is an alkyl or a cycloaliphatic radicalwhich is the decarboxylated residue derived from a diacid, with theproviso that at least one of R³ or R⁴ is a cycloalkyl group.

A preferred cycloaliphatic polyester is PCCD having recurring units offormula (VIII)

wherein in the formula (VII) R³ is a cyclohexane ring, and wherein R⁴ isa cyclohexane ring derived from cyclohexanedicarboxylate or a chemicalequivalent thereof and is selected from the cis- or trans-isomer or amixture of cis- and trans-isomers thereof. Cycloaliphatic polyesterpolymers can be generally made in the presence of a suitable catalystsuch as a tetra(2-ethyl hexyl)titanate, in a suitable amount, generallyabout 50 to 400 ppm of titanium based upon the total weight of the finalproduct.

It is generally desirable for the number average molecular weight(M_(n)) of the polyester to be about 500 to about 1,000,000 grams/mole(g/mole). Within this range, it is desirable to have a number averagemolecular weight of greater than or equal to about 1,000, preferablygreater than or equal to about 5,000 g/mole, and more preferably greaterthan or equal to about 10,000 g/mole. Also desirable is a number averagemolecular weight of less than or equal to about 200,000, preferably lessthan or equal to about 100,000, more preferably less than or equal toabout 75,000 g/mole, and most preferably less than or equal to about60,000 g/mole. An exemplary number average molecular weight for thepolyester is about 40,000 to about 55,000 g/mole.

PCCD generally forms suitable mixtures with the polycarbonate. It isgenerally desirable for a polycarbonate-PCCD mixture to have a meltvolume rate of greater than or equal to about 5 cubic centimeters/10minutes (cc/10 min or ml/10 min) to less than or equal to about 150cubic centimeters/10 minutes when measured at 265° C., at a load of 2.16kilograms and a four minute dwell time. Within this range, it isgenerally desirable to have a melt volume rate of greater than or equalto about 7, preferably greater than or equal to about 9, and morepreferably greater than or equal to about 10 cc/10 min when measured at265° C., at a load of 2.16 kilograms and a four minute dwell time. Alsodesirable within this range, is a melt volume rate of less than or equalto about 125, preferably less than or equal to about 110, and morepreferably less than or equal to about 100 cc/10 minutes.

In general, it is desirable for the polycarbonate-PCCD mixture to have aglass transition temperature of less than or equal to about 205° C.,preferably less than or equal to about 175° C., and more preferably lessthan or equal to about 150° C., and most preferably less than or equalto about 95° C.

Another preferred polyester that may be mixed with other polymers ispolyarylates. Polyarylates generally refers to polyesters of aromaticdicarboxylic acids and bisphenols. Polyarylate copolymers that includecarbonate linkages in addition to the aryl ester linkages, are termedpolyester-carbonates, and may also be advantageously utilized in themixtures. The polyarylates can be prepared in solution or by the meltpolymerization of aromatic dicarboxylic acids or their ester formingderivatives with bisphenols or their derivatives.

In general, it is preferred for the polyarylates to comprise at leastone diphenol residue in combination with at least one aromaticdicarboxylic acid residue. The preferred diphenol residue, illustratedin formula (IX), is derived from a 1,3-dihydroxybenzene moiety, referredto throughout this specification as resorcinol or resorcinol moiety.Resorcinol or resorcinol moieties include both unsubstituted1,3-dihydroxybenzene and substituted 1,3-dihydroxybenzenes.

In formula (IX), R is at least one of C₁₋₁₂ alkyl or halogen, and n is 0to 3. Suitable dicarboxylic acid residues include aromatic dicarboxylicacid residues derived from monocyclic moieties, preferably isophthalicacid, terephthalic acid, or mixtures of isophthalic and terephthalicacids, or from polycyclic moieties such as diphenyl dicarboxylic acid,diphenylether dicarboxylic acid, and naphthalene-2,6-dicarboxylic acid,and the like, as well as combinations comprising at least one of theforegoing polycyclic moieties. The preferred polycyclic moiety isnaphthalene-2,6-dicarboxylic acid.

Preferably, the aromatic dicarboxylic acid residues are derived frommixtures of isophthalic and/or terephthalic acids as generallyillustrated in formula (X).

Therefore, in one embodiment the polyarylates comprise resorcinolarylate polyesters as illustrated in formula (XI) wherein R and n arepreviously defined for formula (IX).

wherein R is at least one of C₁₋₁₂ alkyl or halogen, n is 0 to 3, and mis at least about 8. It is preferred for R to be hydrogen. Preferably, nis zero and m is about 10 and about 300. The molar ratio of isophthalateto terephthalate is about 0.25:1 to about 4.0:1.

In another embodiment, the polyarylate comprises thermally stableresorcinol arylate polyesters that have polycyclic aromatic radicals asshown in formula (XII)

wherein R is at least one of C₁₋₁₂ alkyl or halogen, n is 0 to 3, and mis at least about 8.

In another embodiment, the polyarylates are copolymerized to form blockcopolyestercarbonates, which comprise carbonate and arylate blocks. Theyinclude polymers comprising structural units of the formula (XIII)

wherein each R¹ is independently halogen or C₁₋₁₂ alkyl, m is at least1, p is about 0 to about 3, each R² is independently a divalent organicradical, and n is at least about 4. Preferably n is at least about 10,more preferably at least about 20 and most preferably about 30 to about150. Preferably m is at least about 3, more preferably at least about 10and most preferably about 20 to about 200. In an exemplary embodiment mis present in an amount of about 20 and 50.

Yet another preferred thermoplastic polymer is a copolymer ofpolycarbonate and polysiloxane. The polysiloxane polymer used in thecopolymer generally has a viscosity of about 100 to 1,000,000 poise at25° C. and has chain substituents selected from the group comprising ofhydride, methyl, ethyl, propyl, vinyl, phenyl, and trifluoropropyl. Theend groups on the polysiloxane polymer may be hydride, hydroxyl, vinyl,vinyl diorganosiloxy, alkoxy, acyloxy, allyl, oxime, aminoxy,isopropenoxy, epoxy, mercapto groups, or other known, reactive endgroups.

The thermoplastic polymers may be mixed in any desired suitable ratiosto form the polymeric mixture. Binary mixtures, ternary mixtures andmixtures having more than three polymers may also be used in thepolymeric mixtures. When a binary mixture or ternary mixture is used inthe polymeric mixture, one of the polymers in the mixture may compriseabout 1 to about 99 weight percent (wt %) based on the total weight ofthe composition. Within this range, it is generally desirable to havethe one of the polymers in an amount greater than or equal to about 20wt %, preferably greater than or equal to about 30 wt % and morepreferably greater than or equal to about 35 wt %, based on the totalweight of the composition. Also desirable within this range, is anamount of less than or equal to about 90 wt %, preferably less than orequal to about 80 wt %, and more preferably less than or equal to about70 wt % based on the total weight of the composition. A preferredmixture comprises 60 wt % polycarbonate and 40 wt % PCCD. When ternarymixtures having more than three polymers are used, the various polymersmay be present in any desirable weight ratio.

In order to manufacture the appliance, it is generally desirable toshape the mixture into a sheet. The sheets used in the manufacture ofthe appliance may be of a uniform thickness or of a variable thickness.When the sheet generally has a uniform thickness prior to being formedinto the appliance, it is to be noted that the sheet thickness willgenerally vary after being formed into the appliance. The thickness ofthe sheet is generally selected to provide for ease of repositioning aswell as for ease of comfort. The sheet may have a thickness of about 125(5 mils) to about 1,250 (50 mils) micrometers. Within this range, athickness of greater than or equal to about 200 micrometers, preferablygreater than or equal to about 350 micrometers, more preferably greaterthan or equal to about 400 micrometers may be used. Also desirablewithin this range, is a thickness of less than or equal to about 1,000micrometers, preferably less than or equal to about 950 micrometers andmore preferably less than or equal to about 875 micrometers. Anexemplary thickness is about 700 micrometers to about 800 micrometers.

It is generally desirable for the polymeric mixture to have a tensilestrength and modulus effective to reposition the teeth in the oralcavity over a period of time. The tensile modulus of the material shouldbe adjusted so that the appliance can be installed and removed withoutcausing damage to the patient's oral cavity. It is preferred for thepolymeric mixture to have an elastic modulus of about 1,500Newton/square millimeter (N/mm²) to about 2,500 N/mm² when measured intensile deformation at a rate of 2 millimeters/minute at roomtemperature prior to insertion in the oral cavity. In general, a tensilestrength of greater than or equal to about 1,600 N/mm², preferablygreater than or equal to about 1,650 N/mm², and more preferably greaterthan or equal to about 1,700 N/mm²is suitable.

It is also generally desirable for the polymeric mixture to displaystress retention for purposes of successfully repositioning the teeth inthe oral cavity. It is generally desirable for the polymeric mixture tohave a percent stress retention of greater than or equal to about 50%,preferably greater than or equal to about 60%, more preferably greaterthan or equal to about 70%, and even more preferably greater than orequal to about 75% of the applied stress, when stressed for a period of12 hours, prior to use in the oral cavity.

It is also desirable for the polymeric mixture to be stain resistant.Stain resistance is desirable for cosmetic and aesthetic reasons. Stainresistance is expressed as Delta E and is the difference in color priorto immersion in a staining agent (e.g., coffee, wine, tomato sauces, andthe like) and after immersion in a staining agent followed by thewashing of the mixture in a detergent. It is generally desirable to havea Delta E of less than or equal to about 2, preferably less than orequal to about 1.5, more preferably less than or equal to about 1.0, andeven more preferably less than or equal to about 0.75.

It is further desirable for the polymeric mixture to have a yellownessindex of less than or equal to about 1 and a percent haziness of lessthan or equal to about 0.5 prior to use in the oral cavity. Within therange for yellowness index, it is generally desirable to have a value ofless than or equal to about 0.8, preferably less than or equal to about0.7, and more preferably less than or equal to about 0.6, while having ahaze of less than 0.45, preferably less than or equal to about 0.42, andmore preferably less than or equal to about 0.4, when the sheet has athickness of up to about 500 micrometers. An exemplary value ofyellowness index is about 0.35 to about 0.45 and an exemplary value ofhaze is about 0.23 to about 0.3 prior to introduction into the oralcavity.

While it is generally desirable for the mixture to be transparent, itmay also be opaque if desired. A patient may use opaque appliances afterdark, when the appearance of the appliance is not of paramountimportance. In addition, opaque appliances may be worn by patientsduring periods of sleep, when the appliance is not likely to be noticed.

In one embodiment, the appliance may comprise additional layers disposedupon the sheet comprising the polymeric mixture. The additional layersmay comprise a first layer disposed upon a surface of the sheetcomprising the polymeric mixture, and an optional second layer disposedupon a surface of the sheet opposite the surface in contact with thefirst layer. The additional layers generally comprise an organic polymerhaving a tensile modulus of less than or equal to about 1,000 N/mm².Preferred organic polymers for the additional layers are elastomers.Suitable examples of elastomers for the first layer and/or second layerinclude silicones, fluoroelastomers, styrene-butadienes,styrene-isoprenes, polybutadienes, polyisobutylenes, polyurethanes,chlorosulfonates, butyls, neoprenes, nitriles, polyisoprenes,plasticized nylons, polyesters, polyvinyl ethers, polyvinyl acetates,polyisobutylenes, ethylene vinyl acetates, copolyester ethers,polyolefins, and polyvinyl chlorides, copolymer rubbers such asethylene-propylene (EPR), ethylene-propylene-diene monomer (EPDM),copolyester ethers, styrene-isoprene-styrene (SIS),styrene-butadiene-styrene (SBS), nitrile-butadienes (NBR) andstyrene-butadienes (SBR), mixtures such as ethylene propylene dienemonomer (EPDM), EPR, or NBR, and mixtures and copolymers thereof. Apreferred elastomer for the first layer is a copolyester ether. Anotherpreferred organic polymer for the first layer and/or second layer isPCCD. When the appliance comprises only one additional layer, (e.g., afirst layer), it is generally desirable to place the appliance in themouth of the patient in such a manner so that the first layer contactsthe gums of the patient. Since the first layer generally comprises asofter material than the polymeric mixture it can be used effectively toalleviate pain, discomfort and bleeding gums. A preferred elastomer isECDEL 9966 commercially available from Eastman Chemical Company atKingsport, Tenn.

In one embodiment, the polymeric mixture and/or the elastomer maycontain additives such as mold release agents, pigments, dyes, impactmodifiers, lubricants, anti-oxidants, anti-ozonants, anti-microbials,flame retardants, visual effect additives, fibers, nanotubes, antistaticagents, plasticizers, fillers, and the like, as well as combinations ofone of the foregoing additives.

In certain applications it may be desirable to add fibers to thepolymeric mixture. The fibers may be in the form of whiskers, needles,rods, tubes, strands, elongated platelets, lamellar platelets,ellipsoids, micro fibers, nanofibers and nanotubes, elongatedfullerenes, and the like, as well as combinations comprising at leastone of the foregoing. The fibers may also include short inorganicfibers, mineral fibers single crystal fibers, metal fibers, textileglass fibers and the like, as well as combinations comprising at leastone of the foregoing fibers.

Also included are natural organic fibers such as, for example, woodflour obtained by pulverizing wood, and fibrous products such ascellulose, cotton, sisal, jute, cloth, hemp cloth, felt, and naturalcellulosic fabrics such as Kraft paper, cotton paper and glass fibercontaining paper, starch, cork flour, lignin, ground nut shells, corn,rice grain husks, and the like, as well as combinations comprising atleast one of the foregoing.

Synthetic reinforcing fibers such as, for example, fibers manufacturedfrom polyethylene terephthalate, polybutylene terephthalate and otherpolyesters, polyarylates, polyethylene, polyvinylalcohol,polytetrafluoroethylene, acrylic resins, aromatic polyamides,polyaramids, polybenzimidazoles, polyphenylene sulfides, polyether etherketone, polybenzoxazoles, aromatic polyimides, polyetherimides, and thelike, as well as combinations comprising at least one of the foregoingreinforcing fibers may also be incorporated into the polymeric mixture.

Fibers may be provided in the form of monofilament or multifilamentfibers and can be used either alone or in combination with other typesof fiber, through, for example, co-weaving, core/sheath, side-by-side,orange-type or matrix and fibril constructions, or by other methods usedin fiber manufacture. Typical cowoven structures include glassfiber-carbon fiber, carbon fiber-aromatic polyimide fiber, and aromaticpolyimide fiber-glass fiber. Fibers may be supplied in the form of, forexample, rovings, woven fibrous reinforcements, such as 0 to 90 degreefabrics, non-woven fibrous reinforcements such as continuous strand mat,chopped strand mat, tissues, papers, felts and 3-dimensionally wovenreinforcements, performs and braids.

In general, the amount of fibrous filler present in the polymericmixture can be up to about 50 wt %, based on the total weight of thepolymeric mixture. Within this range, it is generally desirable to havefibrous fillers present in amounts of greater than or equal to about 2wt %, preferably greater than or equal to about 5 wt %, preferablygreater than or equal to about 10 wt %, and more preferably greater thanor equal to about 20 wt %, based on the total weight of the polymericmixture.

In order to make a suitable appliance for repositioning the teeth, it isgenerally desirable to have the polymeric mixture in the form of asheet. A polymeric mixture may generally be formed into a sheet bymixing the polymers in a device that can impart shear to the polymers.Suitable devices are extruders such as single and twin-screw extruders,Buss kneaders, roll mills, helicones, and the like. It may be desirableto couple a twin screw extruder with a single screw extruder to mix thepolymers prior to calendaring the mixture in a roll mill. Thecalendaring of the mixture facilitates the production of the sheet. Inone embodiment, it is generally desirable to form the sheet on a rollmill wherein the mating surfaces of the rolls are both polished. Such asheet is termed a polish/polish sheet. Sheets having a matte/polishfinish may also be used. After the manufacture of the sheet, it may beformed into an appliance for repositioning the teeth as detailed below.The forming of the appliance may be accomplished by process such asthermoforming, molding, and the like, which are discussed in detailbelow.

FIG. 2 is a schematic depicting the procedure by which the appliancesmay be manufactured in order to effect the repositioning of the teeth.As a first step, an initial digital data set (IDDS) representing theinitial tooth arrangement is obtained. The IDDS may be obtained in avariety of ways. For example, the patient's teeth may be scanned orimaged using methods such as x-rays, three-dimensional x-rays,computer-aided tomographic images or data sets, magnetic resonanceimages, and the like, as well as combinations comprising at least one ofthe foregoing methods. The IDDS may also be made after first obtaining aplaster cast of the patient's teeth. After the plaster cast is obtained,it can be digitally scanned using a laser scanner or another rangeacquisition system to produce the IDDS. The data set obtained by therange acquisition system may be converted to other formats so as to becompatible with the software which is used for manipulating imageswithin the data set, as described in more detail below.

There are a variety of range acquisition systems, generally categorizedby whether the process of acquisition requires contact with thethree-dimensional plaster cast. A contact-type range acquisition systemutilizes a probe, having multiple degrees of translational and/orrotational freedom. By recording the physical displacement of the probeas it is drawn across the sample surface, a computer-readablerepresentation of the sample object is made. A non-contact-type rangeacquisition device can be either a reflective-type or transmissive-typesystem. There are a variety of reflective systems in use. Some of thesereflective systems utilize non-optical incident energy sources such asmicrowave radiation or sonar. Others utilize optical energy. Thesenon-contact-type systems working by reflected optical energy furthercontain special instrumentation configured to permit certain measuringtechniques to be performed (e.g., imaging radar, triangulation andinterferometry).

A preferred range acquisition system is an optical or laser basedoptical, reflective, non-contact-type scanner. Non-contact-type scannersare preferred because they are inherently nondestructive (i.e., do notdamage the sample object), are generally characterized by a highercapture resolution and scan a sample in a relatively short period oftime. One such scanner is the Cyberware Model 15 manufactured byCyberware, Inc., Monterey, Calif. Either non-contact-type orcontact-type scanners may also include a color camera, that whensynchronized with the scanning capabilities, provides a means forcapturing, in digital format, a color representation of the plastercast.

In one embodiment, multiple dental images having incrementally differinggeometries may be produced by non-computer-aided techniques. Forexample, plaster casts obtained as detailed above, may be cut usingknives, saws, or other cutting tools in order to permit repositioning ofindividual teeth within the casting. The disconnected teeth may then beheld in place by soft wax or other malleable material, and a pluralityof intermediate tooth arrangements can then be prepared using such amodified plaster casting of the patient's teeth. The differentarrangements can be used to prepare sets of multiple appliances,generally as described below, using pressure and vacuum formingtechniques.

In another embodiment, the manipulation of the IDDS may be accomplishedat a computer or workstation having a suitable graphical user interface(GUI) and software appropriate for viewing and modifying the images. Inthis approach, individual teeth and other components will be “cut” topermit their individual repositioning or removal from the digital data.Additional data, such as patient clinical data, geometrical condition ofthe teeth, material properties relating to the appliances, may be inputinto a computer algorithm for facilitating repositioning of the teeth.After thus “freeing” the components, the user will often follow aprescription or other written specification provided by the treatingprofessional. Alternatively, the user may reposition them based on thevisual appearance or using rules and algorithms programmed into thecomputer. Once the user is satisfied with the final arrangement, thefinal tooth arrangement is incorporated into a final digital data set(FDDS). The IDDS and the FDDS may then be used to generate a pluralityof intermediate digital data sets (INTDDS's). The INTDDS's are generatedto correspond to successive intermediate tooth arrangements. A system ofincremental position adjustment appliances can then be fabricated basedon the INTDDS's, as described below. In general, it is desirable for thesystem to contain at least one or more INTDDS's, preferably 2 or moreINTDDS's, more preferably 10 or more INTDDS's, and more preferably 25 ormore INTDDS's.

Once the intermediate and final data sets have been created, theappliances may be fabricated as illustrated in FIG. 3. Preferably,fabrication methods will employ a rapid prototyping device 200 such as astereolithography machine. A particularly suitable rapid prototypingmachine is Model SLA-250/50, commercially available from 3D System,Valencia, Calif. The prototyping machine 200 will receive the individualdigital data sets and produce one structure corresponding to each of thedesired appliances. As stated above, the appliances are produced fromthe polymeric mixture.

The rapid prototyping machine 200 may alternatively be used to producemolds, which are, in effect, positive tooth models (replicas) of eachsuccessive stage of the treatment. The positive tooth models may then beused to produce the appliance. The positive tooth models are generallymade from plaster, epoxy, and the like. The appliance is generallymanufactured by processes such as injection molding, compressionmolding, vacuum forming, blow molding, and the like. Suitable formingequipment is available under the trade name BIOSTAR from Great LakesOrthodontics, Ltd., Tonawanda, N.Y. The forming machine 250 produceseach of the appliances directly from the positive tooth model and thedesired material. Suitable vacuum forming machines are available fromRaintree Essix, Inc. Metairie, La. These machines may operated in abatch or a continuous fashion.

The thermoforming of the appliance from the sheet is generally carriedout at a surface temperature of about 120° C. to about 180° C. Thesurface temperature referred to herein is the temperature at the surfaceof the sheet during the forming process. Within this range it isgenerally desirable to use temperatures of greater than or equal toabout 125° C., preferably greater than or equal to about 128° C., andmore preferably greater than or equal to about 130° C. Also desirablewithin this range are temperatures of less than or equal to about 178°C., preferably less than or equal to about 175° C., and more preferablyless than or equal to about 170° C. An exemplary thermoformingtemperature is about 135° C. to about 150° C.

It is generally desirable to complete the thermoforming in as short atime as possible to improve efficiency of the manufacturing process. Thetime period for thermoforming a single appliance is about 5 seconds toabout 40 seconds. Within this range, it is generally desirable tothermoform an appliance for greater than or equal to about 7 seconds,preferably greater than or equal to about 10 seconds, and morepreferably greater than or equal to about 12 seconds. Also desirablewithin this range is a time period of less than or equal to about 38seconds, preferably less than or equal to about 34 seconds, and morepreferably less than or equal to about 30 seconds.

After manufacturing, the plurality of appliances is preferably suppliedto the treating professional all at one time. The appliances will bemarked in some manner, generally by sequential numbering directly on theappliances or on tags, pouches, or other items which are affixed to orwhich enclose each appliance, to indicate their order of use. Theappliances are utilized in such a manner to reposition the patient'steeth progressively toward the final tooth arrangement.

The appliance provides a number of advantages over braces. It isaesthetically pleasing and does not undergo any staining while in themouth. In general, no wires or other means will be provided for holdingthe appliance in place over the teeth. In some cases, however, it willbe desirable to provide individual anchors on teeth with correspondingreceptacles or apertures in the appliance 100 so that the appliance canapply an upward force on the tooth that would not be possible in theabsence of such an anchor.

The following examples, which are meant to be exemplary, not limiting,illustrate compositions and methods of manufacturing some of the variousembodiments of the appliances using various materials and apparatus.

EXAMPLES Example 1

This example was undertaken to compare the properties of apolycarbonate-PCCD mixture with the properties of the constituentpolymers, polycarbonate and PCCD, respectively. The polycarbonate usedwas PC100 commercially available from GE Plastics. Two types of PCCDwere used, PCCD4000 having a number average molecular weight (M_(n)) of47,000 g/mole and PCCD6000 having a number average molecular weight of51,500 g/mole. The polycarbonate and the PCCD were first mixed in a50:50 or a 60:40 weight ratio in a 92 millimeter (mm) Werner andPfleiderer (mega-compounder) twin screw extruder. The PC100 sample isdesignated Comparative Sample #1, while the PCCD4000 and PCCD6000samples have been designated Comparative Sample #2 and ComparativeSample #3 respectively. The sample containing the polycarbonate and PCCDin the 50:50 weight ratio is designated Sample #4, while the samplecontaining the polycarbonate and PCCD in the 60:40 weight ratio isdesignated Sample #5.

A quencher comprising phosphoric acid was used to minimize any reactionbetween the polycarbonate and the PCCD. A radical scavenger comprisingphosphonous acid ester was added to the mixture. No UV inhibitors wereused in these examples. The mixture was first pelletized and dried at atemperature of about 82° C. (180° F.) for 6 hours. The dried pelletswere then extruded in a single screw extruder having a 4.5 inch (11.43centimeters) screw diameter. The single screw extruder was a singlestage, barrier type extruder with a length to diameter ratio (L/D) of24:1 and with a flex lip die. The extrusion conditions are shown inTable 1. TABLE 1 Parameter Value Extruder diameter (inches) 4.5 Dryingtemperature (° C.) 82.22 Drying Time (hours) 6 Extruder Temperatures (°C.) Pre-set Zone 1 (° C.) 207.22 Zone 2 (° C.) 215.56 Zone 3 (° C.)221.67 Zone 4 (° C.) 235.00 Zone 5 (° C.) 252.22 Adapter Temperature (°C.) 243.33 Die Lips Temperature (° C.) 252.78 Screw RPM 24.3 ExtraderAmps 212 Screen mesh 105 Roll Stack Temperature (° C.) 26/90 Roll #3Temperature (° C.) 148.9 Production speed (feet/min) 7.6

The extrudate from the single screw extruder was fed into a 3-roll,cooled roll stack for purposes of calendaring into a film. The rollstack had one oil cooled roll having an outer sleeve of silicon basedrubber and one highly polished oil cooled roll. The sheet emerging fromthe roll stack was a matt/polish sheet having a thickness of 750micrometers (30 mils).

The sheet thus obtained was then subjected to a tensile test as per ASTMD 882 in an instron at a rate of 50 mm/minute at room temperature todetermine the tensile modulus, tensile strength, and elongation atyield. The results of these tests are shown in Table 2. TABLE 2Comparative Comparative Comparative Sample 1 Sample 2 Sample 3 Sample 4Sample 5 Resin PC100 PCCD4000 PCCD6000 PC/PCCD PC/PCCD (50/50) (60/40)Tensile Modulus (N/mm²) 1743.94 1046.12 1027.80 1612.44 1748.11 TensileStrength at Yield 57.72 34.21 33.75 47.54 52.91 (N/mm²) Elongation atYield (%) 6.95 3.84 3.94 4.66 5.60 Tensile Strength at Break 63.53 37.8936.92 51.23 56.80 (N/mm²) Elongation at Break (%) 69.14 269.61 237.82122.24 107.95

From the Table 2 it may be seen that the Samples 4 and 5 have comparabletensile properties with the polycarbonate resin of Comparative Sample 1.The tensile properties of the Samples 4 and 5 are superior toComparative Samples 2 and 3, which were made from PCCD.

The samples were then subjected to thermal tests to determine thethermoforming performance of the materials. The glass transitiontemperature (T_(g)) was measured in a Dynamic Mechanical Analyzermanufactured by TA Instruments. The rate of temperature change was 3°C./minute and the frequency applied was 1 hertz (Hz).

The results are shown in Table 3. TABLE 3 Comparative ComparativeComparative Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Resin PC100PCCD4000 PCCD6000 PC/PCCD PC/PCCD (50/50) (60/40) Tg (° C.) 145.00 65.0065.00 111.00 120.00 Power heaters 100.00 70.00 70.00 100.00 100.00 (%)*Forming 203.00 195.00 193.00 180.00 180.00 temperature (° C.) Heatingtime 35.00 40.00 45.00 20.00 20.00 (seconds) Cooling time 10.00 40.0040.00 10.00 10.00 (seconds) Visual Excellent Acceptable AcceptableExcellent Excellent Observations part/ part/ part/ part/ part/homogenous hazy sample hazy sample homogenous homogenous distributiondistribution/ distribution/ optical optical performance performance isexcellent is excellent*indicates the wattages consumed in performing the heating experiment.

Table 3 shows that the mixtures of Samples 4 and 5 have higher glasstransition temperatures than Comparative Samples 2 and 3. In addition,the thermoforming temperature for the mixtures of Samples 4 and 5 is 23°C. lower than the thermoforming temperature of the Comparative Sample 1,which contains only polycarbonate. Lower thermoforming temperatures areadvantageous when the sheet is to be deformed over dental mold material.The lower thermoforming temperature reduces fitting corrections due thedifference in the coefficient of thermal expansion of the material ofthe appliance and the mold material. This also improves dimensionalstability and insures a good and easy fit to patient's teeth.

The sheets were also subjected to stress relaxation tests using a 1%constant strain in a flexural mode. The stress relaxation test wasconducted to determine the force retention of the sheets. This percentforce retention provides information about the resiliency of thematerial that facilitates the repositioning of the tooth duringtreatment. These stress relaxation tests were conducted in a DMA 2980(commercially available from TA Instruments, New Castle, Del.) for atime period of 3 hours or 12 hours. The percentage of stress relaxationis measured by the ratio of stress in the sheet at 3 hours or 12 hoursto the original stress generated in the sheet upon the application ofthe 1% constant strain. The results are shown in Table 4. TABLE 4Comparative Comparative Comparative Sample 1 Sample 2 Sample 3 Sample 4Sample 5 Resin PC100 PCCD4000 PCCD6000 PC/PCCD PC/PCCD (50/50) (60/40)Stress Relaxation 85 43 27 76 80 (% Force Retention) after 3 hr StressRelaxation 79 31 14 67 73 (% Force Retention) after 12 hr

From the Table 4 it may be seen that the percent force retentiondisplayed by the Sample 4 and 5 are similar to those of ComparativeSample 1. The force retention demonstrated by the samples is alsosufficient to engineer a specific stress relaxation profile for clinicaltreatments that may be used to facilitate repositioning the teeth indifficult cases involving missing teeth, deteriorated gums and the like,while at the same time improving clinical treatment efficacy and patientcomfort.

The sheets were also subjected to color and optical property tests todetermine the aesthetic appearance of the appliance when applied in apatient's oral cavity (i.e., mouth) to reposition the teeth. The colorwas measured on a MacBeth 7000A using a reflection mode with a whitecalibration tile as the background. The test was performed as per ASTM D1003. The observer angle was 10 and 65 degrees respectively. The resultsare shown in Table 5. TABLE 5 Comparative Comparative Comparative Sample1 Sample 2 Sample 3 Sample 4 Sample 5 Resin PC100 PCCD4000 PCCD6000PC/PCCD PC/PCCD (50/50) (60/40) Illume D65 D65 D65 D66 D67 L* 95.6195.43 95.42 95.21 95.22 a* −0.44 −0.44 −0.45 −0.38 −0.39 b* 1.80 2.292.47 1.51 1.52 % LT (Transmissivity) 91.70 93.17 93.07 92.00 91.77 %Haziness 0.15 0.31 0.19 0.31 0.26 Yellowness Index 0.60 0.70 0.80 0.100.40L* = extent of lightness;a* = extent of redness;b* = extent of yellowness

From the Table 5, it may seen that the yellowness index for the Sample 4and 5 are surprisingly better than Comparative Samples 1, 2 and 3. Alower yellowness index indicates a reduced tendency to undergoyellowing, and this makes the appliance aesthetically pleasing.

The sheets were also subjected to staining tests to determine the stainresistance properties. It is generally desirable to use sheets thatdisplay a reduced ability to undergo staining upon exposure to a varietyof edibles (e.g., food and drink). The staining agents were EZ Brewcoffee using a normal brewing cycle and “Ragu, Old World Style,Traditional” tomato sauce. The samples were tested as follows. At least2 inches (5.1 centimeters) of a 3 inch (7.5 centimeters) strip of samplewas immersed in the staining agents at a temperature of 37° C. for 3days. The results were reproduced three times for each sample and theresults were averaged. The samples were placed at least 0.25 inch (0.6centimeters) apart. The color was measured on the samples before theimmersion in the staining agent and again after removal from thecontainer having the staining agent. The exposed samples were washedwith water and a mild detergent (e.g., Dawn) prior to drying and makingthe measurements. The results are shown in the Table 6. TABLE 6Comparative Comparative Comparative Sample 1 Sample 2 Sample 3 Sample 4Sample 5 Resin PC100 PCCD4000 PCCD6000 PC/PCCD (50/50) PC/PCCD (60/40)Coffee Delta E 0.17 1.67 0.32 0.17 0.21 Ragu Delta E 0.05 1.87 1.93 0.170.09

Table 6 shows the Delta E for each sample subjected to the stainingagent. The Delta E reflects the difference in color between themeasurements made on a sample prior to staining and after washing withthe detergent. A high value of Delta E reflects a strong ability toretain stains. From Table 6, it maybe seen that Samples 4 and 5 showvery little effects of staining when compared with the ComparativeSamples 2 and 3. The Samples 4 and 5 show similar values to theComparative Sample 1. These low values of stain retention make themixture very useful for use in the appliances since the presence ofstains on any device inserted into the oral cavity is aestheticallyunpleasing.

The aforementioned example shows that an mixture of polycarbonate andPCCD in a weight ratio of 50:50 or 60:40 may be advantageously used asan appliance for repositioning teeth since the mixture possesses aunique combination of desirable properties such as a tensile strength ofgreater than or equal to about 1,500 N/mm², a stain resistance Delta Eof less than or equal to about 2, thermoformability temperatures of lessthan or equal to about 130° C., and a high percent force retention ofgreater than or equal to about 60%. This combination of properties makesthe polycarbonate-PCCD mixture very useful for dental applications wherethe unique combination of tensile strength, force retentioncapabilities, and stain resistance enable an appliance manufactured fromthe mixture to reposition teeth while at the same time beingaesthetically and cosmetically pleasing.

Example 2

This example was undertaken to demonstrate how polycarbonate-PCCDmixtures having different molecular weights have advantageous propertiesthat make them useful for appliances that may be used for repositioningteeth. The number average molecular weights for the respectivepolycarbonate and PCCD components used in the mixtures are shown in theTable 7. The samples of the individual polycarbonate and PCCD componentswere extruded in the manner detailed in Example 1. However the extrudatewas then injection molded into dog bone samples and subjected to tensiletests in the same manner as detailed in Example 1. These results arealso shown in Table 7. TABLE 7 Tensile Elongation at Elongation atComposition M_(n) (g/mole) Modulus (psi) yield (%) break (%) PC-1 9,0002303 7.0 135 PC-2 12,500 2303 7.0 135 PC-3 15,000 2303 7.0 110 PCCD-247,000 986 4.8 215 PCCD-3 51,000 993 4.8 215

The results shown in the Table 7 demonstrate that while tensile modulusand elongation at yield do not vary much with the molecular weight ofthe polycarbonate and the PCCD, the elongation at break for thepolycarbonate is susceptible to a change in the molecular weight between12,500 and 15,000 grams/mole (g/mole).

The polycarbonate and the PCCD components of the Table 7 were mixed inextruders in weight ratios of 50:50, 60:40 and 70:30 respectively, inthe manner detailed in Example 1. The samples were then injection moldedinto test specimens. Phosphonous acid ester and phosphoric acid (10 wt %solution in water) were added to the mixture during the extrusion. Thecompositions are shown in Table 8. TABLE 8 Composition A B C PC-1 orPC-2 or 69.8 59.8 49.8 PC-3 (wt %) PCCD-2 or PCCD- 29.9 39.9 49.8 3 (wt%) Phosphonous acid 0.1 0.1 0.1 ester (PEPQ) (wt %) Phosphoric acid0.225 0.225 0.225 (10% sol. in water) (wt %)

The resulting molded samples were subjected to tensile tests as per ASTMD 638. The results of these tests are shown in Table 9. TABLE 9 PC/PCCDPC- PCCD- Modulus Elongation at Elongation at ratio type type (N/mm²)Yield (%) break (%) 50/50 PC-1 PCCD-2 1625.6 5.70 160.42 50/50 PC-1PCCD-3 1637.8 5.70 160.42 50/50 PC-2 PCCD-2 1618.4 5.68 160.42 50/50PC-2 PCCD-3 1630.6 5.68 160.42 50/50 PC-3 PCCD-2 1619.2 5.82 167.3350/50 PC-3 PCCD-3 1623.6 5.82 165.30 60/40 PC-1 PCCD-2 1743.9 6.00148.42 60/40 PC-1 PCCD-3 1756.0 6.00 148.42 60/40 PC-2 PCCD-2 1762.25.82 148.42 60/40 PC-2 PCCD-3 1774.4 5.82 148.42 60/40 PC-3 PCCD-21756.3 6.00 152.19 60/40 PC-3 PCCD-3 1760.7 6.00 151.28 70/30 PC-1PCCD-2 1862.1 6.30 136.42 70/30 PC-1 PCCD-3 1874.3 6.30 136.42 70/30PC-2 PCCD-2 1906.0 5.96 136.42 70/30 PC-2 PCCD-3 1918.1 5.96 136.4270/30 PC-3 PCCD-2 1893.4 6.18 137.04 70/30 PC-3 PCCD-3 1897.9 6.18137.25

From the Table 9, it may be seen that while an increase in thepolycarbonate increases the elastic modulus, an increase in the PCCDcontent increases the elongation at break.

The glass transition temperature for the molded samples was alsodetermined since it plays an important role in the use of the materialin the application. As stated above, a lower glass transitiontemperature and a lower thermoforming temperature generally facilitatean easier deformation of the sheet over dental mold material. The lowerthermoforming temperature reduces fitting corrections due the differencein the coefficient of thermal expansion of the appliance material andthe mold material. It is generally desired for the glass transitiontemperature of the material of the appliance to be less than that ofpolycarbonate. The glass transition temperature was measured in aDynamic Mechanical Analyzer manufactured by TA Instruments. The rate oftemperature change was 3° C./minute and the frequency rate was 1 Hz. Theresults are shown in Table 10. TABLE 10 PC/PCCD ratio PC-type PCCD-typeTg (° C.)) 50/50 PC-1 PCCD-2 109.8 50/50 PC-1 PCCD-3 109.8 50/50 PC-2PCCD-2 111.7 50/50 PC-2 PCCD-3 111.7 60/40 PC-1 PCCD-2 118.1 60/40 PC-1PCCD-3 118.1 60/40 PC-2 PCCD-2 119.9 60/40 PC-2 PCCD-3 119.9 70/30 PC-1PCCD-2 126.2 70/30 PC-1 PCCD-3 126.2 70/30 PC-2 PCCD-2 128.0 70/30 PC-2PCCD-3 128.0

From the Table 10 it may be seen that the glass transition temperatureof the mixtures is at least about 25° C. less than the glass transitiontemperature of the polycarbonate and these lower glass transitiontemperatures can facilitate the thermoforming of the sheet over a moldof a dental image.

As noted above, it is desirable for the material of the appliance todisplay a percent stress retention effective to facilitate therepositioning of the teeth. Since each appliance is used to repositionthe teeth over a period of time, it is desirable for the sheet todisplay a high percent stress retention (e.g., greater than of equal toabout 60%) over the course of the utility of the appliance in the oralcavity. The samples shown in the Table 11 were subjected to stressretention tests for 12 hours in a manner similar to that detailed inExample 1. The results are shown in the TABLE 11 PC/PCCD-ratio PC-typePCCD-type Stress retention (%) 100/0  PC-2 — 87.2  0/100 — PCCD-2 25.5 0/100 — PCCD-3 36.0 60/40 PC-2 PCCD-3 78.4 50/50 PC-2 PCCD-2 73.22

From the table it may be seen that the mixtures have a higher percentstress retention than the samples containing only PCCD. Further it maybe noted that the mixtures have a percent stress retention of greaterthan or equal to about 60%, which makes them useful in dental appliancesfor repositioning teeth.

The sheets were also subjected to studies to determine their opticalclarity, yellowness index, and the like. The test methodology isdetailed in Example 1. The results are shown in the Table 12. TABLE 12PC/PCCD ratio PC-type PCCD-type YI Transmission Haze 50/50 PC-1 PCCD-22.65 89.2 1.89 50/50 PC-1 PCCD-3 2.65 89.2 2.1 50/50 PC-2 PCCD-2 2.6589.2 1.89 50/50 PC-2 PCCD-3 2.65 89.2 2.1 60/40 PC-1 PCCD-2 2.65 89.21.63 60/40 PC-1 PCCD-3 2.65 89.2 1.72 60/40 PC-2 PCCD-2 2.65 89.2 1.6360/40 PC-2 PCCD-3 2.65 89.2 1.72 70/30 PC-1 PCCD-2 2.65 89.2 1.34 70/30PC-1 PCCD-3 2.65 89.2 1.37 70/30 PC-2 PCCD-2 2.65 89.2 1.34 70/30 PC-2PCCD-3 2.65 89.2 1.37YI = yellowness index

From the Table 12, it may be seen that the yellowness index and thetransmission of the sheet does not change with either molecular weightor the weight ratio of the polycarbonate of the PCCD in the mixture. Aslight decrease in haze is observed with the increase in the molecularweight of the polycarbonate as well as with the increase in the weightfraction of polycarbonate.

The sheets were also subjected to lipid resistance tests. The lipidresistance test is conducted as per ISO 4599. Molded tensile bars wereplaced under fixed strains and contacted with a paper that was immersedin the lipids. The tensile properties are measured prior to and aftercontacting the paper and the results are compared. The paper wascontacted with the neck of the molded tensile bar, wrapped in aluminumfoil and sealed in a plastic bag. The contact period can vary from 3 to7 days. The results shown in Table 13 were for samples tested fortensile properties after 3 days. TABLE 13 PC/PCCD Yield stressElongation @ ratio PC-type PCCD-type retention break retention 100/0 PC-2 — 94.8 89.9 50/50 PC-2 PCCD-2 93.4 43.5 60/40 PC-2 PCCD-2 95.1 97.1

From the table it may be seen that ratio of the respective components inthe mixture plays an important role in the retention of the elongationat break. From Examples 1 and 2, it may be seen that mixtures ofpolycarbonate and PCCD, in weight ratios of 50:50, 60:40, and 70:30,respectively display suitable properties for manufacturing a dentalappliances for repositioning the teeth. As noted above, these mixturespermit the manufacturing of appliances that can facilitate therepositioning of the teeth, while presenting an aesthetically pleasingappearance. In addition, they can be thermoformed at temperatures ofless than or equal to about 130° C., which permits the manufacturing ofappliances that can be tailored to adequately fit a patients oralcavity.

The mixtures of polycarbonate and PCCD are also superior in theirmechanical and optical properties to other commercially available dentalproducts and appliances, which are primarily elastomeric in nature. Ingeneral the superior mechanical properties of the mixtures ofpolycarbonate and PCCD over other commercial appliances permits asmaller number of appliances to be utilized since each appliance can beused for longer periods of time. The transparency of the mixtures ofpolycarbonate and PCCD also make them more aesthetically pleasing thanthe commercially available appliances.

Example 3

In this example, a sheet made from a polycarbonate-PCCD mixture in a60:40 weight ratio (Sample 5 from Example 1) was compared with apolyester urethane sheet. The polyester urethane sheet is commerciallyavailable as ISOPLAST 2530 from Dow Chemical at Midland, Mich. Thesheets both had thicknesses of 30 mils (750 micrometers) and were madein the manner described in Example 1. The polycarbonate-PCCD had amatte/polish finish, while the polyester urethane sheet had apolish/polish finish. The sheets were subjected to stress retention andto stain resistance tests as detailed in Example 1. The results areshown in Table 14. TABLE 14 Comparative Example Sample 5 Resin PC/PCCDPolyester (60/40) Urethane Stress Relaxation (% Force 89 78 Retention)after 3 hr Stress Relaxation (% Force 83 72 Retention) after 12 hrCoffee Delta E 0.21 0.57 Ragu Delta E 0.09 0.49

From the table it may be seen that both the stress retention and thestain resistance of the polycarbonate-PCCD mixture are superior to thepolyester urethane mixture.

From the above experiments it may be seen that the sheets of thepolycarbonate-PCCD mixture have a value of stress retention of greaterthan or equal to about 0.6, a stain resistance that is greater than apolyester urethane mixture, tensile properties that facilitate therepositioning of the teeth in less than or equal to about 40 steps. Thepolymeric mixtures may also be used in other dental applications such asdental retainer appliances that may be used for retaining teeth in adesired position as well as other devices that can be used to preventpatients from grinding their teeth during their sleep.

While the invention has been described with reference to an exemplaryembodiment, it will be understood by those skilled in the art thatvarious changes may be made and equivalents may be substituted forelements thereof without departing from the scope of the invention. Inaddition, many modifications may be made to adapt a particular situationor material to the teachings of the invention without departing from theessential scope thereof. Therefore, it is intended that the inventionnot be limited to the particular embodiment disclosed as the best modecontemplated for carrying out this invention, but that the inventionwill include all embodiments falling within the scope of the appendedclaims.

1. A method for maintaining or repositioning teeth in the oral cavitycomprising: placing an appliance in a patient's mouth; wherein theappliance comprises a polymeric shell that comprises a polymericmixture; and wherein the polymeric shell has cavities designed toreceive teeth; and further wherein the polymeric mixture comprises apolycarbonate and a cycloaliphatic polyester; wherein the polycarbonateis present in an amount of about 50 wt % to about 90 wt %; and whereinthe weight percents are based on a total weight of a mixture thatcomprises polycarbonate and cycloaliphatic polyester.
 2. The method ofclaim 1, wherein additional appliances may be placed in a patient'smouth, and wherein a tooth position defined by a single cavity in eachsuccessive appliance differs from that defined in a prior appliance byan amount of no more than 2 millimeters.
 3. The method of claim 1,further comprising obtaining an initial digital data set (IDDS)representing an initial tooth arrangement.
 4. The method of claim 1,wherein the initial tooth arrangement is obtained by using x-rays,three-dimensional x-rays, computer-aided tomographic images or datasets, magnetic resonance images, or a combination comprising at leastone of the foregoing.
 5. The method of claim 3, wherein the initialtooth arrangement is obtained from a plaster cast of a patient's teeth.6. The method of claim 3, wherein the initial tooth arrangement isobtained in a digital format.
 7. The method of claim 3, furthercomprising producing multiple dental images wherein each successivedental image has an incrementally different geometry for a set of apatient's teeth.
 8. The method of claim 6, further comprisingrepositioning an individual tooth in the initial tooth arrangementobtained in digital format.
 9. The method of claim 5, further comprisingrepositioning an individual tooth in the initial tooth arrangementobtained in a plaster cast of a patient's teeth.
 10. The method of claim3, further comprising obtaining a final digital data set (FDDS)representing an initial tooth arrangement.
 11. A method of manufacturingan appliance comprises: mixing two or more thermoplastic polymers in amelt blending device to form a polymeric mixture; wherein the polymericmixture comprises a polycarbonate and a cycloaliphatic polyester;wherein the polycarbonate is present in an amount of about 50 wt % toabout 90 wt %; and wherein the weight percents are based on a totalweight of a mixture that comprises polycarbonate and cycloaliphaticpolyester. forming the polymeric mixture into a sheet; and thermoformingthe sheet over a replica of a patient's teeth.
 12. The method of claim11, wherein the thermoforming is conducted at a temperature of about 120to about 180° C.
 13. The method of claim 11, wherein the thermoformingis accomplished in about 5 to about 40 seconds.
 14. An articlemanufactured by the method of claim 11.